Dyeing hair with aqueous solution of phenyl-toluyl-or pyridyl amino base compound and benzimidazole coupler

ABSTRACT

A composition for dyeing keratinic fibers comprises a mixture of a base compound having an aromatic nucleus substituted by (1) either two amino groups or (2) by an amino group and a hydroxyl group, the substituents being in the ortho or para position relative to each other, and, as a coupler, a benzimidazole derivative. The weight ratio of the base to the coupler in the composition generally ranges between 1:1 to 1:30 The composition is applied to the hair, preferably at a pH of 8-10 in amounts sufficient to dye the hair and in the presence of an oxidizing agent such as hydrogen peroxide.

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til States Patent ite Kalopissis et al.

DYEING HAIR WITH AQUEOUS SOLUTION 0F PHENYL-TOLUYL-OR PYRIDYL AMINO BASECOMPOUND AND BENZIMIDAZOLE COUPLER Inventors: Gregoire Kaloplssis,Paris; Andree Bugaut,

Boulogne sur Seine, both of France Assignee: Societe Anonyme dite:LOreal, Paris,

France Filed: June 12, 1969 Appl. No.: 832,867

Foreign Application Priority Data June 14, 1968 Luxembourg ..5627l US.Cl ..8/ll, 8/39, 8/43,

' 260/3092 Int. Cl. ..D06p 1/32 Field of Search ..3/l1, 32; 260/3092;96/100 References Cited FOREIC ENPATENTS OR APPLICATIONS 23,193 10/1905GreatBritain ..s/32 1,001,496 3/1965 Great Britain PrimaryExaminer-George F. Lesmes Assistant Examiner-Patricia C. IvesAttorney-Holcombe, Wetherill & Brisebois ABSTRACT A composition fordyeing keratinic fibers comprises a mixture of a base compound having anaromatic nucleus substituted by (1) either two amino groups or (2) by anamino group and a hydroxyl group, the substituents being in the ortho orpara position relative to each other, and, as a coupler, a benzimidazolederivative. The weight ratio of the base to the coupler in thecomposition generally ranges between 1:1 to 1:30 The composition isapplied to the hair, preferably at a pH of 8-10 in amounts sufficient todye the hair and in the presence of an oxidizing agent such as hydrogenperoxide.

6 Claims, No Drawings DYEKNG HAIR WITH AQUEOUS SOLUTION OF PHENYL-TOLUYL-OIR PYRlDYL AMINO BASE COMPOUND AND BENZIMIDAZOLE COUPLER SUMMARYOF THE INVENTION It is conventional to use dyeing compositionscontaining oxidation dyes (commonly known as bases) and especiallyaromatic ortho or para diamines and ortho or para aminophenols, fordyeing keratinic fibers, and particularly human hair. The shadesobtained with these bases have been varied by using color modifiers orcouplers, and in particular aromatic meta diamines and metaaminophenols.

It is the object of the present invention to provide a new class ofcouplers" which may be used with known oxidation dyes.

The present invention accordingly relates to a new article ofmanufacture which consists of a composition for dyeing keratinic fibers,and particularly human hair, which composition is essentiallycharacterized by the fact that it contains:

1. At least one base selected from the group consisting of compoundshaving molecules which contain an aromatic nucleus having either twoamino groups or one amino group and a hydroxyl group in ortho or paraposition with respect to each other. These amino groups may beunsubstituted and/or substituted amino groups and the term amino is usedin its broad sense. Illustrative substituted amino groups include, a1-kylamino, dialkylamino, carbamylamino, aminoalkylamino, etc.

2. At least one coupler consisting of a benzimidazole responding to thegeneral formula:

in which X represents a hydroxyl radical or -Nl-l group, R R R and Rrepresent hydrogen or a methyl radical, with at least one of R and Rbeing hydrogen, and R represents hydrogen or an alkyl radical having 1to 4 carbon atoms. It will be appreciated that the compounds of formula(1) may be used in the form of their acid salts and preferably theirhalohydric acid salts, such as l-lCl H Br, etc.

Among the bases which may advantageously be used with the couplers offormula (1) are: paraphenylene-diamine, paratolylenediamine,paraaminophenol, N-methylparaarninophenol, chloro-pataphenylene-diamine,methoxypara-phenylene-diamine,6-methoxy-3-methyl-para-phenylene-diamine,(Nethyl'N-carbamyl-methyl)-para-phenylene-diamine, and2,5-diamino-pyridine.

Among the couplers of formula (I) are 4-hydroxy-benzimidazole,2-methyl-4-hydroxy-benzimidazole, (4-hydroxy-7- methyl-benzimidazole),2-methyl-4-amino-benzimidazole, 1- methyl-4-hydroxy-benzimidazole,1-buty1-4-hydroxybenzimidazole.

1n the hair dyeing compositions according to the invention, the ratiobetween the base and coupler may vary within broad limits. The preferredratio range is l/1 to 1/3 and in general an excess of coupler ispreferred.

The hair dyeing compositions according to the invention may containother dyes suitable for use under the same conditions, such as directdyes (eg azo or anthraquinone dyes) or dyes obtained by combining basesand couplers other than those to which the present invention isdirected.

The compositions according to the invention may also contain wettingagents, dispersing agents, penetrating agents, or other ingredientsconventionally used in dyeing hair. They may take the form of an aqueoussolution, a cream, or a gel.

The dyeing compositions according to the invention are used in the usualmanner at an alkaline pH, preferably between 8 and 10, which pH may beobtained for example, by

adding ammonia, and the compositions are applied to the hair in thepresence of an oxidizing solution, which is preferably a hydrogenperoxide solution.

The new couplers according to the invention make it possible to obtain avery broad range of colors, extending from blonde to blues to gray.

It is a further object of the present invention to provide the newarticle of manufacture which consists of those of the above-definedcompounds in which the substituent X is a hydroxyl group.

The invention also includes a method of preparing the new compoundscharacterized by the fact that a compound having the following formulais treated at reflux with hydrobromic acid.

(|)CHa In this formula the symbols R R R and R, respond to thedefinition hereinbefore given, either directly, or after reaction withan alkylation agent, R 2, in which Z represents a halogen.

Representative examples of the preparation of new couplers and thepreparation of dyeing compositions containing them will now be givenpurely by way of illustration. The percentages are given in terms ofparts or percentages by weight, and the temperatures in degreescentigrade.

EXAMPLE 1 Preparation of 4hydroxy-benzimidazo1e hydrobromide The processis started with 4-methoxybenzimidazo1e (Melts at a product which isdescribed in known chemical literature, and is obtained by heating2,3-diamino anisole dihydrochloride in the presence of formic acid.

(4-methoxy-benzimidazo1e Chem. Abst. 48-6436h and 4-methoxy 2-methylbenzimidazole J. Pharm. and Pharmaco] 8 661 1956) 0.075 mo1s(1 1.1 g) of4-methoxy benzimidazole is heated at reflux for 5 hours in 50 cm ofbromohydric acid (density 1.78). After cooling, 15.5g of 4-hydroxybenzimidazole hydrobromide is separated out by drying. Afterrecrystallization in bromohydric acid this melts with decomposition at275-278.

Calculated by Analysis C,H-,N O Br Found C 39.07 39.06 H 3.25 3.30 N13.02 13.21

EXAMPLE 2 Preparation of 2-methyl-4-hydroxy benzimidazole hydrobromideThe process is started with 2-methyl-4-methoxy benzimidazole (whichmelts at 164), a product which is described in known literature, whichis obtained by heating 2,3-diamino anisole dihydrochloride in aceticacid.

0.063 mols (10.2g) of 2-methyl-4-methoxy benzimidazole is heated toreflux in 45 cm of hydrobromic acid (density 1.78). After cooling,drying yields 12.5g of 2-methyl-4- hydroxy-benzimidazole hydrobromidewhich, after recrystal lization in hydrobromic acid, melts withdecomposition at 276-280.

Calculated for Analysis C,,H,,N,O Br Found C 41.92 41.63-41.64 H 3.933.83-4.01 N 7r 12.22 12.11

EXAMPLE 3 Preparation of 4-hydroxy-7-methyl benzimidazole hydrobromideThe starting product is 2,3-dinitro-4-methyl anisole (which melts at 133C), which product is described in chemical literature and may beobtained by nitrating 3-nitro-4-methyl anisole.

The dinitro derivative is reduced to 2,3-diamino-4-methyl anisole andthis orthodiamine is then transformed by the conventional Phillippprocess into 4-methoxy-7-methyl benzimidazole which, after treatmentwith hydrobromic acid, yields 4-hydroxy-7-methyl-benzimidazolehydrobromide.

FIRST STEP Preparation of 2,3-diamino-4-methyl anisole dihydrochloride0.05 mols (10.6g) of 2,3-dinitro-4-methyl anisole is added little bylittle, while stirring, to a mixture containing 29.4g of powdered zincand 0.5g of ammonium chloride in 165 cm of absolute alcohol and 42 cm ofwater, which mixture has first been heated to 70 C. When the reductionhas been completed the reaction mixture is dried and the filtrateintroduced into 35 cm of concentrated hydrochloric acid which has firstbeen cooled to 10. After a night at 10, it is dried and after washingwith acetone the yield is 10.4g of 2,3-diamino-4- methylanisoledihydrochloride.

SECOND STEP Preparation of 4-methoxy-7-methyl benzimidazole 0.0462 mols(10.4g) of 2,3-diamino-4-methyl anisole dihydrochloride is heated forfour hours at reflux in 70 cm of formic acid.

This is vacuum dried and the residue is dissolved in 50 cm of water, andalkalized with ammonia. Drying yields 6g of 4- methoxy-7-methylbenzimidazole which, after recrystallization in propyl alcohol, melts at233.

The molecular weight, as determined by potentiometric measurement,was162.

THIRD STEP Preparation of 4-hydroxy-7-methyl benzimidazole hydrobromide0.03 mols (4.86g) of 4-methoxy-7-methyl benzimidazole is heated atreflux for hours in 20 cm of hydrobromic acid (density 1.78). Aftercooling, drying yields 6.8g of 4- hydroxy-7-methyl benzimidazolebromohydride which, after recrystallization in hydrobromic acid, meltsand decomposes at 268270 (hygro-scopic).

EXAMPLE 4 Preparation of l-methyl-4-hydroxy benzimidazole hydrobromide4-methoxy benzimidazole is treated with methyl iodide to obtainl-methyl-4-methoxy benzimidazole, which is then treated with hydrobromicacid.

FIRST STEP Preparation of 1-methyl-4-methoxy benzimidazole 0.127 mols(18g) of methyl iodide is added to a solution of 0.0845 mols (12.5g) of4-methoxy benzimidazole in 125 cm of absolute alcohol containing 0.127mols (7.1g) of potash. The reaction mixture is left overnight at theambient temperature, and filtered. The alcohol is evaporated and theresidue fractionally distilled under vacuum. The yield is 10.5g of 1-methyl-4-methoxy benzimidazole.

E 0.5 mm= 121*(*Ebullition point under a pressure of 0.5 mm ofmercury.), Melting point 50 SECOND STEP Preparation ofl-methyl-4-hydroxy benzimidazole hydrobromide 0.064 mols (10.49 g) ofl-methyl-4-methoxy benzimidazole is heated at reflux for four hours in45 cm of hydrobromic acid (density 1.78). After cooling, drying yields8g of lmethyl-4-hydroxy benzimidazole hydrobromide, which melts 5 anddecomposes at 230232.

EXAMPLE 5 Preparation of 1-buty1-4-hydroxy benzimidazole hydrobromide4-methoxy benzimidazole is treated with butyl bromide to obtainl-butyl-4-methoxy benzimidazole, which is then treated with hydrobromicacid.

l 5 FIRST STEP Preparation of l-buty1-4-methoxy benzimidazole 0.063 mols(8.63g) of normal butyl bromide is added to a solution of 0.042 mols(6.26g) of 4-methoxy benzimidazole in 35 cm" of absolute alcoholcontaining 0.063 mols (3.53g) of potash. The reaction mixture is heatedat reflux for 3 hours, cooled and filtered. The alcohol is filtered andthe residue is fractionally distilled under vacuum. The yield is 6.52gof lbutyl-4-methoxy benzimidazole in the form of a thick colorless oil.E 0.5 mm 160.

SECOND STEP Preparation of l-butyl-4-hydroxy benzimidazole hydrobro-0.048 mols (9.73 g) of 1-butyl-4-methoxy-benzimidazole is heated atreflux for four hours in cm of hydrobromic acid (density 1.78). Aftercooling, drying yields 8.20 g of l-butyl- 4-hydroxy benzimidazolehydrobromide which melts and decomposes at l54-157.

EXAMPLE 6 The following dyeing solution is prepared:

hydrogen peroxide and left 30 minutes on 100 percent white hair. Theresult is a reddish chestnut color, which is stable when exposed to thelight.

EXAMPLE 7 The following dyeing solution is prepared:

2-methyl-4-amino-5-methoxy aniline 1 Paraaminophenol 0 Resorcinol 0. 4hydroxy-7-methyl-benzimidazole 2 Aqueous solution of lauryl ammoniumsulfate (20% lauryl alcohol) Ethylene-diamino-tetraacetic acid soldunder the trademark TRILON B" 20% ammonia sodium bisulfite Water q.s.p.

This solution, mixed weight for weight with 6 percent hydrogen peroxideis left for 30 minutes on 100 percent white hair. The result is a brightgolden chestnut, which is stable when exposed to light.

EXAMPLE 8 The following dyeing solution is prepared:

Paratolylene diamine N-methyl paraaminophenol Resorcinol 0. 4-hydroxybenzimidazole hydrobromide l Lauryl ammonium sulfate solution (20%lauryl alcohol) 2 Ethylene-diamino-tetraacetic acid sold under thetrademark "TRlLON B" O 20% ammonia 1 l 40% sodium bisulfite l Waterq.s.p. 1

This solution, mixed weight for weight with 6 percent hydrogen peroxideis left 30 minutes on 100 percent white hair. The result is aplum-colored chestnut shade which is stable when exposed to the light.

EXAMPLE 9 The following dyeing solution is prepared:

Paratolylene diamine l g 4-hydroxy-7-methyl-benzimidazole 2 g Laurylammonium sulfate solution (20% iauryl alcohol) 20gEthylene-diamino-tetraacetic acid sold under the trademark TRILON B 0.3g 20% ammonia 10 g 40% sodium bisulfite l g Water q.s.p. 100 g Thissolution when mixed weight for weight with 6 percent hydrogen peroxideand applied to 100 percent white hair, yields, at the end of 30 minutesa reddish chestnut which is stable to the light.

EXAMPLE 10 The following dyeing solution is prepared:

2-methyl-4-amino-omethoxy-aniline l.2 g 4-hydroxy-7-methyl-benzimidazole2 g Lauryl ammonium sulfate solution lauryl alcohol) 20 gEthylene-diamino-tetraacetic acid sold under the trademark "TRILON B"0.3 g 20% ammonia 10 g 40% sodium bisulfite l g Water q.s.p. 100 g Thissolution, when mixed weight for weight with 6 percent hydrogen peroxideand applied to 100 percent white hair yields, after minutes, a brightgolden chestnut which is stable when exposed to the light.

This solution, when mixed weight for weight with 6' percent hydrogenperoxide and applied to 100 percent white hair, yields, at the end of 30minutes, a bluish black which is stable when exposed to the light.

EXAMPLE 12 The following dyeing solution is prepared:

2-methyl-4'amino benzimidazole dihydrochloride 0.55 g Para-tolylenediamine 0.53 g 20% ammonia q.s.p. pH 9 Water q.s.p. l00 g This solution,when mixed weight for weight with 6 percent hydrogen peroxide andapplied to 100 percent white hair, yields, after 30 minutes a bluishgreen.

EXAMPLE 13 The following dyeing solution is prepared:

Para-tolylene diamine l 2 2-methyl-4-hydroxy benzimidazole hydrobromide2 g Lauryl ammonium sulfate solution (20% lauryl alcohol) 20 gEthylene-diamino-tetraacetic acid sold under the trademark TRILON B" 0.3g 20% ammonia 10 g 40% sodium bisulfite l g Water q.s.p. I00 g Thissolution, when mixed weight for weight with 6 percent hydrogen peroxideand left for 30 minutes on percent white hair, yields a violet blue.

EXAMPLE 14 The following dyeing solution is prepared:

This solution, when mixed weight for weight with 6 percent hydrogenperoxide and applied to 100 percent white hair, produces, at the end of30 minutes, a deep blue.

The salts that are produced in the foregoing examples may be reconvertedto the corresponding compounds of Formula I in any manner desired. Forexample, l-methyl-4-hydroxybenzimidazole is formed when the hydrobromide salt of example 4 is placed in an ammonia solution having a pHof 8 at 251 F.

What is claimed is:

l. A composition for dyeing keratinic fibers which comprises an aqueoussolution of I a. at least one base compound having an aromatic nucleusselected from group consisting of phenyl and pyridyl, said nucleus beingsubstituted with a set of substituents selected from the groupconsisting of 1) two amino groups and (2) an amino group and a hydroxylgroup, said substituents being in ortho or para position with respect toeach other; and

b. at least one coupler selected from the group consisting of (3) abenzimidazole derivative having the formula:

in which X is selected from the group consisting of hydroxyl and -NH R,,R R and R are selected from the group consisting of hydrogen and methylwith at least one of R, and R representing hydrogen, and R is selectedfrom the group consisting of hydrogen and alkyl having 1 to 4 carbonatoms and (4) the acid salts of said derivative, the weight ratio ofsaid base to said coupler ranging between l:l to l :3.

2. The composition ofclaim 1 in which said base is selected from thegroup consisting of paraphenylenediamine paratolylenediamine,paraaminophenol, N-methyl-paraaminophenol,chloro-para-phenylene-diamine, methoxy-paraphenylene-diamine,6-methoxy-3-methyl-paraphenylenediamine, (N-ethyl,N-carbamylmethyl)-para-phenylenediamine, and 2,5 diaminopyridine.

3. The composition of claim 1 in which said coupler is selected from thegroup consisting of 4-hydroxybenzimidazole,2-methyl-4-hydroxy-benzimidazole, 4-hydroxy-7-methyl-benzimidazole,Z-methyl-4-amino-benzimidazole, l-methyl-4-hydroxy-benzimidazole, andl-butyl-4-hydroxybenzimidazole.

4. The composition of claim 1 having a pH of 8-10.

5. A method of dyeing hair which comprises applying to the hair inamounts sufficient to dye said hair the composition of claim 1 at a pHof 8-10 in the presence ofa solution of an oxidizing agent 6. The methodof claim wherein said oxidizing agent is hydrogen peroxide.

2. The composition of claim 1 in which said base is selected from thegroup consisting of paraphenylenediamine paratolylenediamine,paraaminophenol, N-methyl-para-aminophenol,chloro-para-phenylene-diamine, methoxy-para-phenylene-diamine,6-methoxy-3-methyl-paraphenylene-diamine, (N-ethyl,N-carbamylmethyl)-para-phenylene-diamine, and 2,5 diaminopyridine. 3.The composition of claim 1 in which said coupler is selected from thegroup consisting of 4-hydroxy-benzimidazole,2-methyl-4-hydroxy-benzimidazole, 4-hydroxy-7-methyl-benzimidazole,2-methyl-4-amino-benzimidazole, 1-methyl-4-hydroxy-benzimidazole, and1-butyl-4-hydroxy-benzimidazole.
 4. The composition of claim 1 having apH of 8-10.
 5. A method of dyeing hair which comprises applying to thehair in amounts sufficient to dye said hair the composition of claim 1at a pH of 8-10 in the presence of a solution of an oxidizing agent. 6.The method of claim 5 wherein said oxidizing agent is hydrogen peroxide.